CN107722196B - method for preparing weathered coal humic acid-based super absorbent resin by aqueous solution polymerization method - Google Patents
method for preparing weathered coal humic acid-based super absorbent resin by aqueous solution polymerization method Download PDFInfo
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Abstract
the invention discloses a method for preparing weathered coal humic acid-based super absorbent resin by an aqueous solution polymerization method, which comprises the following steps of firstly, sequentially grinding, sieving and drying weathered coal to obtain weathered coal powder; then, extracting humic acid in the weathered coal powder by a nitric acid oxidation method; and then, taking acrylic acid monomers and humic acid as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator, taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid super absorbent resin in an aqueous solution by an aqueous solution polymerization method. The method takes the aqueous solution as the solvent, is environment-friendly and easy to obtain, has low requirements on equipment, easy control of reaction conditions, low synthesis cost and no pollution, and is easy to realize clean production.
Description
Technical Field
the invention belongs to the technical field of resin material preparation methods, and particularly relates to a method for preparing weathered coal humic acid-based super absorbent resin by an aqueous solution polymerization method.
background
The high water absorption resin is a novel functional polymer material containing strong hydrophilic groups, and forms a three-dimensional network structure through moderate crosslinking, so the high water absorption resin has high water absorption and water retention, can quickly absorb a large amount of water and swell into gel, the gel generated after water absorption and swelling is not easy to separate out water under a pressurized condition, and meanwhile, when the high water absorption resin is in an environment with lower humidity, the high water absorption resin can slowly release the water, and therefore, the high water absorption resin has wide application prospect in the aspects of agriculture and ecological restoration. However, the salt and alkali resistance of the super absorbent resin is poor, which limits the wide application of the super absorbent resin in practice.
humic acid is a mixture of natural macromolecular aromatic compounds and hydroxycarboxylic acids, has various active groups and has various functions. Weathered coal refers to coal exposed to the earth surface or located in a shallow layer of the earth surface, is rich in reserves and wide in distribution in China, is used as a resource which is not reasonably utilized, has high humic acid content, and can be used for synthesizing humic acid super absorbent resin by extracting humic acid from weathered coal, so that reasonable utilization of the resource can be achieved, the water absorption, salt resistance and alkali resistance of the water absorbent resin can be improved, and the cost is greatly reduced.
at present, there are various methods for preparing super absorbent resin, including bulk polymerization, aqueous solution polymerization, and reversed phase suspension polymerization. Compared with other synthesis methods, the aqueous solution polymerization method has low requirements on equipment, easily controlled reaction conditions, low synthesis cost, no pollution and easy realization of clean production.
Disclosure of Invention
the invention aims to provide a method for preparing weathered coal humic acid-based super absorbent resin by an aqueous solution polymerization method.
The technical scheme adopted by the invention is that the method for preparing the weathered coal humic acid based super absorbent resin by an aqueous solution polymerization method is implemented according to the following steps:
step 1, sequentially grinding, sieving and drying weathered coal to obtain weathered coal powder;
step 2, extracting humic acid in the weathered coal powder by a nitric acid oxidation method after the weathered coal powder is obtained in the step 1;
and 3, taking the aqueous solution as a solvent, taking the acrylic acid monomer and the humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator and taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid-based super absorbent resin in the aqueous solution by an aqueous solution polymerization method.
the invention is also characterized in that:
in step 1, a sieve having an average pore size of 180 μm was used for sieving.
in the step 1, the drying temperature is 75-85 ℃, and the drying time is 7-9 h.
in the step 2, humic acid in weathered coal powder is extracted by a nitric acid oxidation method, and the method comprises the following specific steps:
Step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the addition standard is as follows: 2-3 mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
wherein, the mass percentage concentration of the concentrated nitric acid is 65-68% (the nitric acid is not diluted when in use, and is directly taken as a market product);
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxidative decomposition reaction on the weathered coal powder-nitric acid mixed material under a constant-temperature water bath condition to obtain a precipitate;
wherein the temperature of the constant-temperature water bath is 90-110 ℃, and the time of the oxygenolysis reaction is 40-80 min;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the addition standard is as follows: each gram of precursor material A needs 9-11 mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in a vibration mode to obtain a precursor material B;
wherein the molar volume concentration of the sodium hydroxide solution is 0.4-0.5 mol/L;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 90-110 ℃, and the reaction time is 45-55 min; filtering at 40-50 deg.c to collect filtrate and regulating pH to 2 with hydrochloric acid; standing for 24h, filtering, drying, and grinding to obtain humic acid;
the quality of the prepared humic acid is 68.79-72.01% of the consumption of weathered coal.
in the step 3, the humic acid-based super absorbent resin is prepared by an aqueous solution polymerization method, and the method is specifically implemented according to the following steps:
Step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
Step 3.2, preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 35-50%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 0.97-1.1: 1;
Weighing the humic acid obtained in the step 2 according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 3-5% of that of the acrylic acid monomer;
weighing ammonium persulfate according to the mass of the acrylic monomer in the step 3.1, wherein the mass of the ammonium persulfate is 2.1-4.8% of the mass of the acrylic monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
Weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.04-0.12% of the mass of the acrylic acid monomer; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 25-30 ℃ under a stirring state, adding the acrylic monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the mixture is uniformly mixed, then adding all NaOH solution, stirring for 10-15 min, then adding all N, N' -methylene bisacrylamide solution and ammonium persulfate solution, continuously stirring, raising the reaction temperature to 70-80 ℃, keeping the temperature for reaction for 2-4 h, and then forming viscous mass substances in the reaction kettle;
wherein, the NaOH solution, the N, N' -methylene bisacrylamide solution and the ammonium persulfate solution are added in a dropwise manner;
and 3.4, taking out the viscous mass-shaped substance obtained in the step 3.3, cutting into blocks, drying at the temperature of 60-65 ℃ for 24-36 h, cooling, and grinding the blocks to obtain the humic acid-based super absorbent resin.
The invention has the beneficial effects that:
(1) The method for preparing the weathered coal humic acid-based super absorbent resin by the aqueous solution polymerization method, disclosed by the invention, has the advantages that the humic acid raw material for preparing the super absorbent resin is derived from weathered coal, so that the weathered coal which is a resource which is not reasonably utilized is effectively utilized, and the reasonable utilization of the resource is realized;
(2) the method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method takes water as a solvent, is environment-friendly and easily available, and has the advantages of low equipment requirement, easily controlled reaction conditions, low synthesis cost and no pollution, thereby easily realizing clean production;
(3) The humic acid-based high water-absorbent resin prepared by the method has higher water absorption capacity and water absorption rate and stronger salt resistance and acid and alkali resistance;
(4) the method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method can realize the water retention effect of the weathered coal humic acid based super absorbent resin in saline-alkali soil, and has more profound influence on the environmental management of the saline-alkali soil.
Detailed Description
the present invention will be described in detail with reference to the following embodiments.
the method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method comprises the following steps:
step 1, sequentially grinding, sieving and drying weathered coal to obtain weathered coal powder;
wherein, a screen with the average aperture of 180 mu m is adopted during sieving;
the drying temperature is 75-85 ℃, and the drying time is 7-9 h;
step 2, after obtaining weathered coal powder in step 1, extracting humic acid in the weathered coal powder by a nitric acid oxidation method, and the specific steps are as follows:
step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the addition standard is as follows: 2-3 mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
wherein, the mass percentage concentration of the concentrated nitric acid is 65-68% (the nitric acid is not diluted when in use, and is directly taken as a market product);
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxidative decomposition reaction on the weathered coal powder-nitric acid mixed material under a constant-temperature water bath condition to obtain a precipitate;
wherein the temperature of the constant-temperature water bath is 90-110 ℃, and the time of the oxygenolysis reaction is 40-80 min;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the addition standard is as follows: each gram of precursor material A needs 9-11 mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in a vibration mode to obtain a precursor material B;
wherein the molar volume concentration of the sodium hydroxide solution is 0.4-0.5 mol/L;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 90-110 ℃, and the reaction time is 45-55 min; filtering at 40-50 deg.c to collect filtrate and regulating pH to 2 with hydrochloric acid; standing for 24 hours, filtering, drying, and grinding to obtain humic acid, wherein the mass of the prepared humic acid is 68.79-72.01% of the consumption of weathered coal;
step 3, taking an aqueous solution as a solvent, taking an acrylic acid monomer and humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator, taking a sodium hydroxide solution as a neutralizer, and preparing the air-blown coal humic acid-based super absorbent resin in the aqueous solution by an aqueous solution polymerization method, wherein the method is implemented according to the following steps:
step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
step 3.2, preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 35-50%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 0.97-1.1: 1;
weighing the humic acid obtained in the step 2 according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 3-5% of that of the acrylic acid monomer;
weighing ammonium persulfate according to the mass of the acrylic monomer in the step 3.1, wherein the mass of the ammonium persulfate is 2.1-4.8% of the mass of the acrylic monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.04-0.12% of that of the acrylic acid; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 25-30 ℃ under a stirring state, adding the acrylic monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the mixture is uniformly mixed, then adding all NaOH solution, stirring for 10-15 min, then adding all N, N' -methylene bisacrylamide solution and ammonium persulfate solution, continuously stirring, raising the reaction temperature to 70-80 ℃, keeping the temperature for reaction for 2-4 h, and then forming viscous mass substances in the reaction kettle;
The NaOH solution, the N, N' -methylene bisacrylamide solution and the ammonium persulfate solution are added in a dropwise manner, wherein the dropwise adding speed of the NaOH solution is slower, and the reasons are that: NaOH can release a large amount of heat in the reaction;
step 3.4, taking out the viscous mass-shaped substance obtained in the step 3.3, cutting into blocks, drying, cooling, and crushing the blocks to obtain humic acid-based super absorbent resin;
Wherein the drying temperature is 60-65 ℃, and the drying time is 24-36 h.
The weathered coal humic acid-based super absorbent resin prepared by the method has the deionized water absorption rate of 1039.2 g/g-1331.2 g/g and the normal saline (0.9 percent NaCl aqueous solution) absorption rate of 80.4 g/g-87.2 g/g; in addition, the test shows that: when the particle size of the weathered coal humic acid based super absorbent resin is 10-20 meshes, the water absorption multiplying power is the largest, within 120min, the water absorption multiplying power of the weathered coal humic acid based super absorbent resin can reach 70% of saturation, within 300min, the water absorption multiplying power of the weathered coal humic acid based super absorbent resin can reach 90%, the synthesized weathered coal humic acid based super absorbent resin is high in water absorption efficiency, and better in salt resistance and acid and alkali resistance.
Example 1
the method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method comprises the following steps:
step 1, sequentially grinding, sieving and drying weathered coal, wherein a sieve with the average pore diameter of 180 mu m is adopted during sieving, the drying temperature is 75 ℃, and the drying time is 7 hours, so as to obtain weathered coal powder;
step 2, after obtaining weathered coal powder in step 1, extracting humic acid in the weathered coal powder by a nitric acid oxidation method, and the specific steps are as follows:
step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the mass percentage concentration of the concentrated nitric acid is 65%, and the addition standard is as follows: 2mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxygenolysis reaction on the weathered coal powder-nitric acid mixed material for 40min under the condition of a 90 ℃ constant-temperature water bath to obtain a precipitate;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the molar volume concentration of the sodium hydroxide solution is 0.4mol/L, and the addition standard is as follows: each gram of precursor material A needs 9mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in an oscillating mode to obtain a precursor material B;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 90 ℃, and the reaction time is 45 min; filtering at 40 deg.C to collect filtrate, and adjusting pH to 2 with hydrochloric acid; standing for 24h, filtering, drying, and grinding to obtain humic acid, wherein the mass of the prepared humic acid is 68.79% of the consumption of weathered coal;
step 3, taking the aqueous solution as a solvent, taking an acrylic acid monomer and the humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator, taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid super absorbent resin in the aqueous solution by an aqueous solution polymerization method, wherein the preparation method is implemented according to the following steps:
step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
step 3.2, weighing humic acid according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 4% of the mass of the acrylic acid monomer;
Preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 35%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 0.97: 1;
weighing ammonium persulfate and the mass of the ammonium persulfate according to the mass of the acrylic acid monomer in the step 3.1
the amount was 2.1% by mass of the acrylic monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
Weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.04% of the mass of the acrylic acid monomer; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 25 ℃ under a stirring state, adding the acrylic acid monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the acrylic acid monomer is uniformly mixed, then adding all NaOH solution, stirring for 10min, adding all N, N' -methylene bisacrylamide solution and ammonium persulfate solution, continuously stirring, raising the reaction temperature to 75 ℃, keeping the temperature for reaction for 2h, and forming sticky mass substances in the reaction kettle;
adding a NaOH solution, an N, N' -methylene bisacrylamide solution and an ammonium persulfate solution in a dropwise manner;
and 3.4, taking out the viscous mass-shaped substance obtained in the step 3.3, cutting into blocks, drying at the drying temperature of 60 ℃ for 24 hours, and cooling and crushing the blocks to obtain the humic acid-based super absorbent resin.
the weathered coal humic acid-based super absorbent resin obtained by the method has the deionized water absorption capacity of 1039.2g/g and the physiological saline (0.9 percent NaCl aqueous solution) absorption capacity of 83.7 g/g.
example 2
The method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method comprises the following steps:
step 1, sequentially grinding, sieving and drying weathered coal to obtain weathered coal powder, wherein a sieve with the average pore size of 180 mu m is adopted during sieving, the drying temperature is 75 ℃, and the drying time is 8 hours;
step 2, after obtaining weathered coal powder in step 1, extracting humic acid in the weathered coal powder by a nitric acid oxidation method, and the specific steps are as follows:
step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the mass percentage concentration of the concentrated nitric acid is 65%, and the addition standard is as follows: 2.5mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxygenolysis reaction on the weathered coal powder-nitric acid mixed material for 60min under the condition of a constant-temperature water bath at 100 ℃ to obtain a precipitate;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the molar volume concentration of the sodium hydroxide solution is 0.5mol/L, and the addition standard is as follows: each gram of precursor material A needs 10mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in an oscillating mode to obtain a precursor material B;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 100 ℃, and the reaction time is 50 min; filtering at 45 deg.c to collect filtrate, and regulating the filtrate to pH 2 with hydrochloric acid; standing for 24h, filtering, drying, and grinding to obtain humic acid, wherein the mass of the prepared humic acid is 71.54% of the consumption of weathered coal;
step 3, taking the aqueous solution as a solvent, taking an acrylic acid monomer and the humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator, taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid-based super absorbent resin in the aqueous solution by an aqueous solution polymerization method, wherein the preparation method specifically comprises the following steps:
step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
Step 3.2, preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 40%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 1.1: 1;
weighing the humic acid obtained in the step 2 according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 5% of that of the acrylic acid monomer;
Weighing ammonium persulfate according to the mass of the acrylic monomer in the step 3.1, wherein the mass of the ammonium persulfate is 2.1% of the mass of the acrylic monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
Weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.08 percent of the mass of the acrylic acid monomer; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
Step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 25 ℃ under a stirring state, adding the acrylic monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the acrylic monomer is uniformly mixed, then adding all NaOH solution, stirring for 12min, adding all N, N' -methylene bisacrylamide solution and potassium persulfate solution, continuously stirring, heating the reaction temperature to 72 ℃, keeping the temperature for reaction for 2.5 hours, and forming viscous mass substances in the reaction kettle;
Adding a NaOH solution, an N, N' -methylene bisacrylamide solution and an ammonium persulfate solution in a dropwise manner;
and 3.4, taking out the viscous mass-shaped substance obtained in the step 3.3, cutting into blocks, drying at the temperature of 62 ℃ for 30 hours, and cooling and crushing the blocks to obtain the humic acid super absorbent resin.
the weathered coal humic acid-based super absorbent resin obtained by the method has the deionized water absorption capacity of 1331.2g/g and the physiological saline (0.9 percent NaCl aqueous solution) absorption capacity of 87.2 g/g.
example 3
The method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method comprises the following steps:
Step 1, sequentially grinding, sieving and drying weathered coal, wherein a sieve with the average pore diameter of 180 mu m is adopted during sieving, the drying temperature is 80 ℃, and the drying time is 7 hours, so as to obtain weathered coal powder;
step 2, after obtaining weathered coal powder in step 1, extracting humic acid in the weathered coal powder by a nitric acid oxidation method, and the specific steps are as follows:
Step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the mass percentage concentration of the concentrated nitric acid is 66%, and the addition standard is as follows: 3mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxygenolysis reaction on the weathered coal powder-nitric acid mixed material for 80min under the condition of a 90 ℃ constant-temperature water bath to obtain a precipitate;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the molar volume concentration of the sodium hydroxide solution is 0.5mol/L, and the addition standard is as follows: each gram of precursor material A needs 10mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in an oscillating mode to obtain a precursor material B;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 100 ℃, and the reaction time is 55 min; filtering at 40 deg.C to collect filtrate, and adjusting pH to 2 with hydrochloric acid; standing for 24h, filtering, drying, and grinding to obtain humic acid, wherein the mass of the prepared humic acid is 70.94% of the consumption of weathered coal;
step 3, taking the aqueous solution as a solvent, taking an acrylic acid monomer and the humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an alcuric acid solution as an initiator, taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid-based super absorbent resin in the aqueous solution by an aqueous solution polymerization method, wherein the preparation method specifically comprises the following steps:
step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
step 3.2, preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 50%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 1.01: 1;
weighing the humic acid obtained in the step 2 according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 3.5 percent of that of the acrylic acid monomer;
weighing ammonium persulfate according to the mass of the acrylic monomer in the step 3.1, wherein the mass of the ammonium persulfate is 3.0 percent of the mass of the acrylic monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.06% of the mass of the acrylic acid monomer; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
Step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 26 ℃ under a stirring state, adding the acrylic acid monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the acrylic acid monomer is uniformly mixed, then adding all NaOH solution, stirring for 14min, adding all N, N' -methylene bisacrylamide solution and ammonium persulfate solution, continuously stirring, raising the reaction temperature to 74 ℃, keeping the temperature for reaction for 4 hours, and forming viscous mass-shaped substances in the reaction kettle;
adding a NaOH solution, an N, N' -methylene bisacrylamide solution and an ammonium persulfate solution in a dropwise manner;
step 3.3, taking out the viscous mass-shaped substance obtained in the step 3.2, cutting into blocks, drying at the drying temperature of 62 ℃ for 32 hours, and cooling and crushing the blocks to obtain the humic acid-based super absorbent resin;
The deionized water absorption rate of the weathered coal humic acid based super absorbent resin obtained by the method is as follows: 1121.8g/g, and 80.4g/g of absorption capacity of physiological saline (0.9% NaCl aqueous solution).
example 4
the method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method comprises the following steps:
Step 1, sequentially grinding, sieving and drying weathered coal, wherein a sieve with the average pore diameter of 180 mu m is adopted during sieving, the drying temperature is 78 ℃, and the drying time is 7.5 hours, so as to obtain weathered coal powder;
step 2, after obtaining weathered coal powder in step 1, extracting humic acid in the weathered coal powder by a nitric acid oxidation method, and the specific steps are as follows:
step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the mass percentage concentration of the concentrated nitric acid is 67%, and the addition standard is as follows: 2.5mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxygenolysis reaction on the weathered coal powder-nitric acid mixed material for 60min under the condition of 110 ℃ constant-temperature water bath to obtain a precipitate;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the molar volume concentration of the sodium hydroxide solution is 0.5mol/L, and the addition standard is as follows: each gram of precursor material A needs 11mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in an oscillating mode to obtain a precursor material B;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 90 ℃, and the reaction time is 50 min; filtering at 43 deg.C to collect filtrate, and adjusting pH to 2 with hydrochloric acid; standing for 24h, filtering, drying, and grinding to obtain humic acid, wherein the mass of the prepared humic acid is 69.74% of the consumption of weathered coal;
step 3, taking the aqueous solution as a solvent, taking an acrylic acid monomer and the humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator, taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid-based super absorbent resin in the aqueous solution by an aqueous solution polymerization method, wherein the preparation method specifically comprises the following steps:
step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
step 3.2, preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 40%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 1.1: 1;
weighing the humic acid obtained in the step 2 according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 4% of that of the acrylic acid monomer;
weighing ammonium persulfate according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the ammonium persulfate is 3.9 percent of the mass of the acrylic acid monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
Weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.06% of the mass of the acrylic acid monomer; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 28 ℃ under a stirring state, adding the acrylic monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the acrylic monomer is uniformly mixed, then adding all NaOH solution, stirring for 10min, adding all N, N' -methylene bisacrylamide solution and ammonium persulfate solution, continuously stirring, heating the reaction temperature to 78 ℃, keeping the temperature for reaction for 3.3h, and forming a sticky mass substance in the reaction kettle;
Adding a NaOH solution, an N, N' -methylene bisacrylamide solution and an ammonium persulfate solution in a dropwise manner;
and 3.3, taking out the viscous mass-shaped substance obtained in the step 3.2, cutting into blocks, drying at 65 ℃ for 29 hours, and cooling and crushing the blocks to obtain the humic acid-based super absorbent resin.
the weathered coal humic acid-based super absorbent resin obtained by the method has the deionized water absorption capacity of 1163.2g/g and the physiological saline (0.9 percent NaCl aqueous solution) absorption capacity of 85.6 g/g.
Example 5
the method for preparing the weathered coal humic acid based super absorbent resin by the aqueous solution polymerization method comprises the following steps:
step 1, sequentially grinding, sieving and drying weathered coal, wherein a sieve with the average pore diameter of 180 mu m is adopted during sieving, the drying temperature is 85 ℃, and the drying time is 9 hours, so as to obtain weathered coal powder;
step 2, after obtaining weathered coal powder in step 1, extracting humic acid in the weathered coal powder by a nitric acid oxidation method, and the specific steps are as follows:
step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the mass percentage concentration of the concentrated nitric acid is 68%, and the addition standard is as follows: 3mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxygenolysis reaction on the weathered coal powder-nitric acid mixed material for 80min under the condition of a constant-temperature water bath at 100 ℃ to obtain a precipitate;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
Step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the molar volume concentration of the sodium hydroxide solution is 0.4mol/L, and the addition standard is as follows: each gram of precursor material A needs 9mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in an oscillating mode to obtain a precursor material B;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 100 ℃, and the reaction time is 50 min; filtering at 50 deg.C to collect filtrate, and adjusting pH to 2 with hydrochloric acid; standing for 24h, filtering, drying, and grinding to obtain humic acid, wherein the mass of the prepared humic acid is 72.01% of the consumption of weathered coal;
step 3, taking the aqueous solution as a solvent, taking an acrylic acid monomer and the humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator, taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid-based super absorbent resin in the aqueous solution by an aqueous solution polymerization method, wherein the preparation method specifically comprises the following steps:
step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
step 3.2, preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 35%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 0.97: 1;
weighing the humic acid obtained in the step 2 according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 3% of that of the acrylic acid monomer;
weighing ammonium persulfate according to the mass of the acrylic monomer in the step 3.1, wherein the mass of the ammonium persulfate is 3.0 percent of the mass of the acrylic monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.08 percent of the mass of the acrylic acid monomer; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 30 ℃ under a stirring state, adding the acrylic acid monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the acrylic acid monomer is uniformly mixed, then adding all NaOH solution, stirring for 15min, adding all N, N' -methylene bisacrylamide solution and ammonium persulfate solution, continuously stirring, heating the reaction temperature to 80 ℃, keeping the temperature for reaction for 4 hours, and forming viscous mass-shaped substances in the reaction kettle;
adding a NaOH solution, an N, N' -methylene bisacrylamide solution and an ammonium persulfate solution in a dropwise manner;
and 3.3, taking out the viscous mass-shaped substance obtained in the step 3.2, cutting into blocks, drying at 65 ℃ for 36 hours, cooling, and grinding the blocks to obtain the humic acid-based super absorbent resin.
the weathered coal humic acid-based super absorbent resin obtained by the method has the deionized water absorption capacity of 1101.9g/g and the physiological saline (0.9 percent NaCl aqueous solution) absorption capacity of 84.1 g/g.
Claims (6)
1. The method for preparing the weathered coal humic acid-based super absorbent resin by the aqueous solution polymerization method is characterized by comprising the following steps:
step 1, sequentially grinding, sieving and drying weathered coal to obtain weathered coal powder;
Step 2, extracting humic acid in the weathered coal powder by a nitric acid oxidation method after the weathered coal powder is obtained in the step 1; the method comprises the following specific steps:
step 2.1, adding the weathered coal powder obtained in the step 1 into concentrated nitric acid, wherein the addition standard is as follows: 2-3 mL of concentrated nitric acid is needed for each gram of weathered coal powder, and the weathered coal powder and the concentrated nitric acid are uniformly mixed in a vibration mode to obtain a weathered coal powder-nitric acid mixed material;
Wherein, the mass percentage concentration of the concentrated nitric acid is 65-68 percent;
2.2, placing the weathered coal powder-nitric acid mixed material obtained in the step 2.1 in a water bath constant-temperature oscillator, and carrying out an oxidative decomposition reaction on the weathered coal powder-nitric acid mixed material under a constant-temperature water bath condition to obtain a precipitate;
wherein the temperature of the constant-temperature water bath is 90-110 ℃, and the time of the oxygenolysis reaction is 40-80 min;
2.3, performing centrifugal treatment on the precipitate obtained in the step 2.2 to separate solid from liquid; adding deionized water, shaking and mixing uniformly, centrifuging for solid-liquid separation again, repeatedly washing the precipitate to be neutral, and pouring out the liquid to obtain a precursor material A;
Step 2.4, adding the precursor material A obtained in the step 2.3 into a sodium hydroxide solution, wherein the addition standard is as follows: each gram of precursor material A needs 9-11 mL of sodium hydroxide solution, and the precursor material A and the sodium hydroxide solution are uniformly mixed in a vibration mode to obtain a precursor material B;
wherein the molar volume concentration of the sodium hydroxide solution is 0.4-0.5 mol/L;
2.5, carrying out alkali dissolution reaction on the precursor material B obtained in the step 2.4 under the condition of constant-temperature water bath, wherein the alkali dissolution temperature is 90-110 ℃, and the reaction time is 45-55 min; filtering at 40-50 deg.c to collect filtrate and regulating pH to 2 with hydrochloric acid; standing for 24h, filtering, drying, and grinding to obtain humic acid;
step 3, taking an aqueous solution as a solvent, taking an acrylic acid monomer and the humic acid obtained in the step 2 as raw materials, taking an N, N' -methylene bisacrylamide solution as a cross-linking agent, taking an ammonium persulfate solution as an initiator and taking a sodium hydroxide solution as a neutralizer, and preparing the humic acid-based super absorbent resin in the aqueous solution by an aqueous solution polymerization method;
The method is implemented according to the following steps:
Step 3.1, respectively weighing deionized water and acrylic monomers according to the volume ratio of 1:1, and weighing the mass of the weighed acrylic monomers;
Step 3.2, preparing and measuring a sodium hydroxide solution, wherein the neutralization degree of the prepared sodium hydroxide solution is 35-50%, the mass volume concentration of the prepared sodium hydroxide solution is 0.2g/mL, and the volume ratio of the sodium hydroxide solution to the acrylic acid monomer in the step 3.1 is 0.97-1.1: 1;
weighing the humic acid obtained in the step 2 according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the humic acid is 3-5% of that of the acrylic acid monomer;
weighing ammonium persulfate according to the mass of the acrylic monomer in the step 3.1, wherein the mass of the ammonium persulfate is 2.1-4.8% of the mass of the acrylic monomer; uniformly mixing the weighed ammonium persulfate with deionized water to prepare an ammonium persulfate solution with the mass volume concentration of 0.02 g/mL;
Weighing N, N '-methylene bisacrylamide according to the mass of the acrylic acid monomer in the step 3.1, wherein the mass of the N, N' -methylene bisacrylamide is 0.04-0.12% of the mass of the acrylic acid monomer; uniformly mixing the weighed N, N '-methylene bisacrylamide with deionized water to prepare an N, N' -methylene bisacrylamide solution with the mass volume concentration of 0.01 g/mL;
step 3.3, after the steps 3.1 and 3.2, adding humic acid and deionized water in the step 3.1 into a reaction kettle, condensing and refluxing, heating the reaction kettle to 25-30 ℃ under a stirring state, adding the acrylic monomer weighed in the step 3.1 into the reaction kettle after the humic acid and the deionized water in the reaction kettle are fully dissolved, stirring until the mixture is uniformly mixed, then adding all NaOH solution, stirring for 10-15 min, then adding all N, N' -methylene bisacrylamide solution and ammonium persulfate solution, continuously stirring, raising the reaction temperature to 70-80 ℃, and after heat preservation reaction, forming viscous mass substances in the reaction kettle;
and 3.4, taking out the viscous mass-shaped substance obtained in the step 3.3, drying, cooling, and crushing the block-shaped substance to obtain the humic acid-based super absorbent resin.
2. The method for preparing weathered coal humic acid based super absorbent resin according to claim 1, wherein in step 1, a screen with an average pore size of 180 μm is used for sieving.
3. the method for preparing weathered coal humic acid based super absorbent resin by aqueous solution polymerization as claimed in claim 1, wherein in step 1, the drying temperature is 75 ℃ to 85 ℃ and the drying time is 7h to 9 h.
4. the method for preparing weathered coal humic acid based super absorbent resin by aqueous solution polymerization according to claim 1, wherein in step 3.3, the reaction time is kept at 2-4 h.
5. the method for preparing weathered coal humic acid based super absorbent resin by aqueous solution polymerization method according to claim 1, wherein in step 3.3, NaOH solution, N' -methylene bisacrylamide solution and ammonium persulfate solution are all added dropwise.
6. The method for preparing weathered coal humic acid based super absorbent resin by aqueous solution polymerization as claimed in claim 1, wherein in step 3.4, the drying temperature is 60 ℃ to 65 ℃ and the drying time is 24h to 36 h.
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Application publication date: 20180223 Assignee: Pucheng Zhenggong Gas Co.,Ltd. Assignor: XI'AN POLYTECHNIC University Contract record no.: X2023980034729 Denomination of invention: Preparation of weathered coal humic acid based superabsorbent resin by aqueous solution polymerization Granted publication date: 20191210 License type: Common License Record date: 20230418 |
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